Hydrochloric Acid → 2-Chloro-1-(4-methoxyquinolin-2-yl)ethanone

HRID 251745

Reaktionsgleichung

Reaktionsgleichung von HRID 251745
[CH3:1][O:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[N:6]=[C:5]([C:13]([OH:15])=O)[CH:4]=1.C(Cl)(=O)[C:17]([Cl:19])=O.[Si](C=[N+]=[N-])(C)(C)C.CCN(CC)CC.Cl>C(Cl)Cl.CCOCC.CN(C=O)C>[Cl:19][CH2:17][C:13]([C:5]1[CH:4]=[C:3]([O:2][CH3:1])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[N:6]=1)=[O:15]

Komponenten

9

Edukt 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 167693TrimethylsilyldiazomethaneHCID 5945964-Methoxy-2-quinolinecarboxylic acid

Produkt 1

HCID 441579222-Chloro-1-(4-methoxyquinolin-2-yl)ethanone

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a solution of 4-methoxyquinoline-2-carboxylic acid and DMF (50 μL) in DCM at 0° C. was added dropwise oxalyl chloride (1.2 eq). The cooling bath was removed and the mixture was stirred for 2 hr at RT, then the solvent was removed under reduced pressure. The residue was dissolved in THF/MeCN (1:1) and cooled to 0° C., a pre-cooled solution (0° C.) of TMSCHN2 (1.2 eq) and Et3N (1.2 eq) was added dropwise and the resulting mixture was stirred for 2 hr at 0° C. An excess of 2M HCl solution in Et2O was added and the reaction was stirred for further hour at 0° C. and then partitioned between sat. aq. NaHCO3 solution and DCM. The organic phase was separated, dried (Na2SO4), and concentrated under reduced pressure to afford a dark brown solid which was used as such in the next step. 1H NMR (300 MHz, CDCl3) δ: 8.47 (1H, d, J=8.0 Hz), 8.09 (1H, d, J=8.4 Hz), 7.81-7.73 (1H, m), 7.66-7.58 (1H, m), 7.51 (1H, s), 5.31 (2H, s), 4.13 (3H, s). MS (ES) Cl2H10ClNO2 requires: 235, found: 236 (M+H)+.

Aufarbeitung

  1. customThe cooling bath was removed
  2. customthe solvent was removed under reduced pressure
  3. dissolutionThe residue was dissolved in THF/MeCN (1:1)
  4. temperaturecooled to 0° C.
  5. stirringthe resulting mixture was stirred for 2 hr at 0° C
  6. stirringthe reaction was stirred for further hour at 0° C.
  7. custompartitioned between sat. aq. NaHCO3 solution and DCM
  8. customThe organic phase was separated
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated under reduced pressure
  11. customto afford a dark brown solid which

Quellen und Nachweise

ORD-Eintrag
ord-1421c5562ed14f20b58c48b15548d8a1
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07863294B2

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